IL95092A - 1-[(2,4- (Halo or haloalkyl substituted)-phenyl-5-cyclo-alkoxy]pyrazoline-3-carboxylates, their preparation and their use as safeners - Google Patents
1-[(2,4- (Halo or haloalkyl substituted)-phenyl-5-cyclo-alkoxy]pyrazoline-3-carboxylates, their preparation and their use as safenersInfo
- Publication number
- IL95092A IL95092A IL9509290A IL9509290A IL95092A IL 95092 A IL95092 A IL 95092A IL 9509290 A IL9509290 A IL 9509290A IL 9509290 A IL9509290 A IL 9509290A IL 95092 A IL95092 A IL 95092A
- Authority
- IL
- Israel
- Prior art keywords
- formula
- compound
- alkyl
- haloalkyl
- cycloalkyl
- Prior art date
Links
- 125000001188 haloalkyl group Chemical group 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 11
- 125000001475 halogen functional group Chemical group 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 239000004009 herbicide Substances 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 244000038559 crop plants Species 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 9
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 231100000208 phytotoxic Toxicity 0.000 claims abstract description 7
- 230000000885 phytotoxic effect Effects 0.000 claims abstract description 7
- 230000009291 secondary effect Effects 0.000 claims abstract description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 29
- -1 C^-Ce-alkyl Chemical group 0.000 claims description 24
- 230000002363 herbicidal effect Effects 0.000 claims description 18
- 238000009472 formulation Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000011814 protection agent Substances 0.000 claims description 5
- 150000003217 pyrazoles Chemical class 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 claims description 3
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 2
- 101100229907 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) GPP2 gene Proteins 0.000 claims description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002084 enol ethers Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000003223 protective agent Substances 0.000 claims description 2
- FMPJHEINDXIEHS-UHFFFAOYSA-N (2-phenoxyphenyl) hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1OC1=CC=CC=C1 FMPJHEINDXIEHS-UHFFFAOYSA-N 0.000 claims 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical class C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- PQKBPHSEKWERTG-UHFFFAOYSA-N Fenoxaprop ethyl Chemical compound C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 PQKBPHSEKWERTG-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000004495 emulsifiable concentrate Substances 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 240000005979 Hordeum vulgare Species 0.000 description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 description 4
- 244000098338 Triticum aestivum Species 0.000 description 4
- 239000000729 antidote Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229940086542 triethylamine Drugs 0.000 description 3
- 239000004562 water dispersible granule Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- FROBCXTULYFHEJ-OAHLLOKOSA-N propaquizafop Chemical compound C1=CC(O[C@H](C)C(=O)OCCON=C(C)C)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 FROBCXTULYFHEJ-OAHLLOKOSA-N 0.000 description 2
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- DVDKSXXCJZRNES-UHFFFAOYSA-N (2-benzylphenyl) hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1CC1=CC=CC=C1 DVDKSXXCJZRNES-UHFFFAOYSA-N 0.000 description 1
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- DWDIDIITNMWCKN-UHFFFAOYSA-N 2-(N-ethoxy-C-propylcarbonimidoyl)-3-hydroxy-5-(2-phenylsulfanylpropyl)cyclohex-2-en-1-one Chemical compound C1C(=O)C(C(=NOCC)CCC)=C(O)CC1CC(C)SC1=CC=CC=C1 DWDIDIITNMWCKN-UHFFFAOYSA-N 0.000 description 1
- WVQBLGZPHOPPFO-UHFFFAOYSA-N 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(1-methoxypropan-2-yl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(C(C)COC)C(=O)CCl WVQBLGZPHOPPFO-UHFFFAOYSA-N 0.000 description 1
- VONWPEXRCLHKRJ-UHFFFAOYSA-N 2-chloro-n-phenylacetamide Chemical compound ClCC(=O)NC1=CC=CC=C1 VONWPEXRCLHKRJ-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- IRDGHFDTPIJNMU-UHFFFAOYSA-N 2-ethoxy-3-methylbut-1-ene Chemical compound CCOC(=C)C(C)C IRDGHFDTPIJNMU-UHFFFAOYSA-N 0.000 description 1
- ZKJCCGFDBUVUFW-UHFFFAOYSA-N 2-methoxy-3,3-dimethylbut-1-ene Chemical compound COC(=C)C(C)(C)C ZKJCCGFDBUVUFW-UHFFFAOYSA-N 0.000 description 1
- KDMASJAWKNAFBX-UHFFFAOYSA-N 2-methoxy-3-methylbut-1-ene Chemical compound COC(=C)C(C)C KDMASJAWKNAFBX-UHFFFAOYSA-N 0.000 description 1
- XURCTOYGFOIZLA-UHFFFAOYSA-N 4,5-dihydro-1h-pyrazole-5-carboxylic acid Chemical class OC(=O)C1CC=NN1 XURCTOYGFOIZLA-UHFFFAOYSA-N 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 1
- 239000005497 Clethodim Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- GUVLYNGULCJVDO-UHFFFAOYSA-N EPTC Chemical compound CCCN(CCC)C(=O)SCC GUVLYNGULCJVDO-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005600 Propaquizafop Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- YQSGAPRTTCXZBP-UHFFFAOYSA-N [2-(1,3-benzothiazol-2-yloxy)phenyl] hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1OC1=NC2=CC=CC=C2S1 YQSGAPRTTCXZBP-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 229940075522 antidotes Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- VAIZTNZGPYBOGF-UHFFFAOYSA-N butyl 2-(4-{[5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoate Chemical compound C1=CC(OC(C)C(=O)OCCCC)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 VAIZTNZGPYBOGF-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- SILSDTWXNBZOGF-KUZBFYBWSA-N chembl111058 Chemical compound CCSC(C)CC1CC(O)=C(\C(CC)=N\OC\C=C\Cl)C(=O)C1 SILSDTWXNBZOGF-KUZBFYBWSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000007931 coated granule Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- GGWHBJGBERXSLL-UHFFFAOYSA-N cycloxydim Chemical compound C1C(=O)C(C(=NOCC)CCC)=C(O)CC1C1CSCCC1 GGWHBJGBERXSLL-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XQTFGOSTLPHBRA-UHFFFAOYSA-N ethyl 1-(2,4-dichlorophenyl)-5-propan-2-ylpyrazole-3-carboxylate Chemical compound N1=C(C(=O)OCC)C=C(C(C)C)N1C1=CC=C(Cl)C=C1Cl XQTFGOSTLPHBRA-UHFFFAOYSA-N 0.000 description 1
- OWZFULPEVHKEKS-UHFFFAOYSA-N ethyl 2-chloro-2-oxoacetate Chemical compound CCOC(=O)C(Cl)=O OWZFULPEVHKEKS-UHFFFAOYSA-N 0.000 description 1
- OSUHJPCHFDQAIT-UHFFFAOYSA-N ethyl 2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanoate Chemical compound C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 OSUHJPCHFDQAIT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MFSWTRQUCLNFOM-UHFFFAOYSA-N methyl 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoate Chemical compound C1=CC(OC(C)C(=O)OC)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl MFSWTRQUCLNFOM-UHFFFAOYSA-N 0.000 description 1
- MDXGYOOITGBCBW-UHFFFAOYSA-N methyl 2-[4-[4-(trifluoromethyl)phenoxy]phenoxy]propanoate Chemical compound C1=CC(OC(C)C(=O)OC)=CC=C1OC1=CC=C(C(F)(F)F)C=C1 MDXGYOOITGBCBW-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N pent-2-enoic acid Chemical compound CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000005554 pyridyloxy group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D231/08—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with oxygen or sulfur atoms directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Compounds of the formula (I) <IMAGE> (I) where X1 and X2 independently of one another are halogen or haloalkyl, R1 is hydrogen, alkyl or alkoxyalkyl, R2 is alkyl or haloalkyl, and R3 is hydrogen, alkyl, alkenyl or alkynyl, can reduce, or entirely compensate, phytotoxic secondary effects of herbicides on crop plants and are therefore suitable as agents for the selective use of herbicides.
[US5037468A]
Description
95092/2 l-(2 4-(HALO OR HALOALKYL SUBSTITUTED ) -PHENYL-5- ( CYCLO ) ALKOXY-PYRAZOLINE-3-CARBOXYLATES , THEIR PREPARATION AND THEIR USE AS SAFENERS . οη: π,ο·)υί>>ορΊ_η 3 - — Description When plant treatment agents, in particular herbicides, are applied, it is possible that undesired damage occurs on the crop plants, which cannot be tolerated. In particular when herbicides are applied after the crop plants have emerged, it is therefore often desired to avoid the risk of a potential phytotoxicity.
Compounds which have the properties of protecting crop plants against phytotoxic damage by herbicides without adversely affecting the actual herbicidal action in these agents are called "antidotes" or "safeners".
Various compounds have already been described for this application; cf., for example, EP-A 152,006 (= US-A-4,602,932) and EP-A 0,174,562 (= US-A-4 , 639 , 266 ) . 1-Phenyl- and l-(pyrid-2-yl)-pyrazole derivatives were suggested as safeners in German Patent Application P-3 808 896.7 (EP-A 0,333,131).
Only few l-aryl-4 , 5-pyrazoline-3-carboxylic acid derivatives have been disclosed. For example, Kheraze and coworkers (Zh. Org. Khim. 12 (1976) 6, 1332-1337 and Zh. Org. Khim. 14 (1978) 1396-1401) describe pyrazolines of the formulae R = CH3 or i-propyl A biological action of these alkoxypyrazolines has hitherto not been described.
The present invention relates to 4,5-pyrazoline-3-car-: boxylic acid derivatives of the formula (I) where X1 and X2 independently of one another are halogen or haloalkyl, R1 is hydrogen, alkyl, cycloalkyl or alkyloxyalkyl , R2 is alkyl, cycloaklyl or haloalkyl, and R3 is hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl Formula ( I ) in this context comprises all geometric isomers and stereoisomers which are possible. Furthermore, halogen in formula (I) denotes fluorine, chlorine, bromine or iodine, alkyl denotes straight-chain or branched alkyl, alkenyl denotes straight-chain or branched alkenyl, it being possible for the double bond to be in any desired position in the alkenyl radical, and alkynyl denotes straight-chain or branched alkynyl, it being possible in this case too for the triple bond to be located anywhere in the alkynyl radical, and haloalkyl denotes alkyl which is monosubstituted or polysubstituted by halogen.
Compounds of the formula (I) according to the invention where X1 and X2 independently of one another are halogen or Ci-C.-haloalkyl , Rl is Ci-Ce-alkyl, C3-C6-cycloalkyl or (Ci-Ce-alkyloxy) - Cx-Cg-alkyl, R2 is Ci-Cfs-alkyl, C3-C6-cycloalkyl or Cj-Cg-haloalkyl, and R3 is hydrogen, C1-Ca-alkyl, C3-C6-cycloalkyl, C2-C8- alkenyl or C2-C6-alkynyl, are of particular interest.
Haloalkyl is preferably trifluoromethyl, 2-chloroethyl , 1, 1 , 2 , 2-tetrafluoroethyl or hexafluoropropyl , and halogen is preferably fluorine, chlorine or bromine.
Alkyl preferably represents one of the radicals methyl, ethyl, n-propyl, i-propyl", the butyl, pe1ntyl~andTie"xyi isomers. Cycloalkyl preferably represents cyclopentyl and cyclohexyl .
Alkenyl is preferably one of the radicals vinyl, 1- " propen-l-yl, l-propen-2-yl, and the butenyl, pentenyl and hexenyl isomers .
Alkynyl preferably represents acetylenyl, 1-propynyl or 2-propyny1.
Compounds of the formula (I) according to the invention where X1 and X2 independently of one another are fluorine, chlorine, bromine or trifluoromethyl , R1 is Cj-C-alkyl or , R2 is C1-Cj-alkyl which is unsubstituted or monosubsti- tuted or polysubstituted by halogen, and R3 is hydrogen, Ci-C^-alkyl, Ca-C^-alkenyl or C2-C4- alkynyl, are particularly preferred.
The invention furthermore relates to a process for the preparation of the compounds of the formula (I), which comprises reacting a compound of the formula (II) where Y is chlorine or bromine and X1, X2 and R1 have the abovementioned meanings, with enol ethers of the formula (III) (in) H2C=C where R2 and R3 have the abovementioned meanings .
The components can be employed in equimolar amounts or in excess of the compounds of the formula (III), usually in the molar ratio (II): (III) of 1:1.05 to 1:20, preferably in the molar ratio of 1:1.1 to 1:5.
Some of the compounds of the formula (II) are known or can be synthesized by customary processes. For example, they can be obtained from the corresponding anilines by diazotization and coupling with the corresponding 2-chloroacetic esters. The compounds of the formula (III) are likewise accessible by customary processes, for example by eliminating alcohol from the corresponding ketals .
In general, the reaction is carried out at between 0 and 150 °C, advantageously between 20 and 100 eC, if appropriate in the presence of an organic base such as sterically hindered amines, for example triethylamine or pyridine, or of an inorganic base such as, for example, potassium carbonate, potassium hydroxide or sodium carbonate, with or without the presence of an organic solvent such as, if appropriate, a halogenated aliphatic or aromatic hydrocarbon or an ether, for example the solvent toluene, xylene, dichloroethane, dimethoxyethane, diglyme or triglyme, cyclohexane, petroleum ether or chlorobenzene .
Bases and solvents are only enumerated by way of example, without the process being limited to these examples.
By alcohol elimination, the compounds of the formula (I) can be converted into corresponding pyrazole esters, as are described as safeners in German Patent Application P 3,808,896.7 (EP-A-0 , 333 , 131) .
The invention therefore furthermore relates to a process for converting the compounds of the formula (I) into the corresponding pyrazoles, which comprises treating the compounds of the formula (I) without or in the presence of an organic solvent such as, for example, an optionally halogenated aliphatic or aromatic hydrocarbon or an ether, for example the solvent toluene, xylene, chloro-benzene, diglyme or triglyme, if appropriate in the presence of an inorganic or organic acid such as mineral acids or organic sulfonic acids, for example the acids p-toluenesulfonic acid, phosphoric acid, sulfuric acid or trifluoromethanesulfonic acid, at temperatures between 0 and 200 °C, advantageously between 50 and 120 °C, with the elimination of the compound of the formula HOR2 where R2 is as defined in formula (I).
The compounds of the formula (I) have the property of reducing or completely preventing phytotoxic secondary effects of plant protection agents, in particular of herbicides, which can occur when these agents are employed in crops. The compounds of the formula (I) are capable of substantially or completely compensating harmful secondary effects of the herbicides, without impairing the effectiveness of these herbicides against harmful plants. It is possible to considerably enlarge the field of application of conventional herbicides by adding the safener compound of the formula ( I ) .
The present invention therefore also relates to a method of protecting crop plants against phytotoxic secondary effects of plant protection agents, in particular herbicides, which comprises treating the plants, seeds of the plants or areas under cultivation with a compound of the formula (I) before, after, or simultaneously with, the plant protection agent.
Examples of herbicides whose phytotoxic secondary effects can be reduced by means of the compounds of the formula (I) are carbamates, thiocarbamates , haloacetanilides, substituted phenoxy-, naphthoxy- and phenoxyphenoxycar-boxylic acid derivatives as well as heteroaryloxyphenoxy-carboxylic acid derivatives, such as quinolyloxy- , quinoxalyloxy-, pyridyloxy-, benzoxazolyloxy- and benzothiazolyloxy-phenoxycarboxylic acid esters, and furthermore dimedone oxime derivatives. Preferred compounds amongst these are phenoxyphenoxy- and heteroaryl-oxyphenoxy-carboxylic acid esters and structural analogs such as benzylphenoxycarboxylic acid esters. Suitable esters in this connection are, in particular, lower alkyl, alkenyl and alkynyl esters.
The following herbicides may be mentioned by way of example but without imposing any restriction: A) Herbicides of the type of the (Ci-C alkyl, (C2-C -alkenyl or (C3-CJ alkynyl phenoxyphenoxy- and heteroaryl-oxyphenoxy-carboxylates, such as methyl 2-(4-(2,4-di-chlorophenoxy) phenoxy) propionate, methyl 2- ( 4- ( 4-bromo-2-chlorophenoxy) phenoxy) propionate, methyl 2- (4- (4-trifluoromethylphenoxy) phenoxy) propionate, methyl 2- (4-(2-chloro-4-trifluoromethylphenoxy) phenoxy) propionate, methyl 2- ( 4- ( 2, 4-dichlorobenzyl) phenoxy) propionate, 2-isopropylideneaminooxyethyl (R) -2-[4-( 6-chloroquinoxalin-2-yloxy) phenoxy]propionate (propaquizafop) , ethyl 4-(4-(4-trifluoromethylphenoxy) phenoxy) pent-2-enoate, ethyl 2-( 4- ( 3, 5-dichloropyridyl-2-oxy)phenoxy)propionate, propar-gyl 2- ( 4- ( 3 , 5-dichloropyridyl-2-oxy)phenoxy) propionate, ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy)propionate, ethyl 2- ( 4- ( 6-chlorobenzothiazol-2-yloxy)phenoxy)pro-pionate, methyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate, butyl 2- ( 4- ( 5-trifluoro-methyl-2-pyridyloxy) phenoxy) propionate, ethyl 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) -propionate, ethyl 2-(4-( 6-fluoro-2-quinoxalyloxy) phenoxy) propionate , propargyl 2- ( 4- ( 5-chloro-3-fluoropyridyl-2-oxy) phenoxy) propionate, ethyl 2- ( 4- ( 6-chloro-2-quinolyloxy) phenoxy) propionate, trimethylsilylmethyl 2- ( 4- ( 3 , 5-dichloropyridyl-2-oxy) -phenoxy) propionate, ethyl 2-(4-(3-chloro-5-trifluoro- methoxy-2-pyridyloxy) phenoxy)propionate , B) Chloroacetanilide herbicides, such as N-methoxymethyl-2 , 6-diethyl-chloroacetanilide, 2-chloro-N- ( 2-ethyl-6-methylphenyl ) -N- ( 2-methoxy-1-methylethyl ) acetamide, N- ( 3-methyl-1 , 2 , 4-oxadiazol-5-ylmethyl ) -2 , 6-dimethylchloro-acetanilide, C) Thiocarbamates, such as S-ethyl N,N-dipropylthio-carbamate or S-ethyl N,N-diisobutylthiocarbamate, D) Dimedone derivatives, such as 2-(N-ethoxybutyrimi-doyl ) -5- ( 2-ethylthiopropyl) -3-hydroxy-2-cyclohexen-l-one, 2- ( N-ethoxybutyrimidoyl ) -5- ( 2 -phenylthiopropyl ) -3-hydroxy-2-cyclohexen-l-one or 2- ( 1-allyloxyiminobutyl ) -4-methoxycarbonyl-5, 5-dimethyl-3-oxocyclohexenol, 2-(N-ethoxypropionamidoyl ) -5-mesityl-3-hydroxy-2-cyclohexen-1-one (also called 5-(2,4,6-trimethylphenyl)-3-hydroxy- 2- [l-(ethoxyimino) propyl ]cyclohex-2-en-l-one) , 2-(N-ethoxybutyrimidoyl ) -3-hydroxy-5- ( thian-3-yl ) -2-cyclohexen-l-one , 2- [ 1- ( ethoxyimino ) butyl ] -3-hydroxy-5- ( 2H-tetrahydrothiopyran-3-yl) -2-cyclohexen-l-one (BASF 517); ( ±)-2-[ (E) -3-chloroallyloxyiminopropyl] -5- (2-ethylthiopropyl ) -3-hydroxycyclohex-2-enone (clethodim) .
Preferred herbicides which may be mentioned from amongst those which can be combined according to the invention with the compounds of the formula (I) are the compounds listed under A), in particular ethyl 2- ( 4- ( 6-chloro-benzoxazol-2-yloxy) phenoxy)propionate, ethyl 2-(4-(6-chlorobenzothiazol-2-yloxy) phenoxy) propionate and propargyl 2- ( 4- ( 5-chloro-3-fluoropyridyl-2-oxy) phenoxy) -propionate. From the substances mentioned under D) , 2-(N-ethoxypropionamidoyl ) -5-mesityl-3-hydroxy-2-cyclohexen-1-one is particularly important.
The ratio by weight of safener (compound I): herbicide can vary within wide limits and is preferably in the range from 1:10 to 10:1, in particular 2:1 to 1:10.
The amounts of herbicide and safener which are ideal in each case depend on the type of the herbicide used or on the safener used as well as on the nature of the plant canopy to be treated, and they can be determined for each individual case by appropriate experiments.
The safeners are mainly employed in particular in cereal crops (wheat, rye, barley, oats), rice, maize and sorghum, but also in cotton, sugar beet, sugar cane and soya bean.
Depending on their properties, the safeners can be used for pre-treating the seed of the crop plant (seed treatment), or they can be incorporated in the seed furrows prior to sowing, or used together with the herbicide prior to, or after, plant emergence. Pre-emergence treatment includes both the treatment of the area under cultivation prior to sowing and treatment of the areas under cultivation where seed has been sown but growth of the crop plants has not yet taken place.
However, application of the antidote simultaneously with the herbicide in the form of tank mixes or readymixes is preferred.
The compounds of the formula (I) or their combinations with one or more of the herbicides or groups of herbicides mentioned can be formulated in a variety of ways, as predetermined by the biological and/or chemophysical parameters. The following possibilities are therefore suitable for formulation: wettable powders (WP), emulsi-fiable concentrates (EC), aqueous solutions (SL), concentrated emulsions (E ), such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, dispersions on an oil or water base (SC), dusting agents (DP), seed treatment agents, granules in the form of microgranules, spray granules, coated granules and adsorption granules, soil granules and granules for scattering, water-dispersible granules (WG) , ULV formulations/ microcapsules or waxes.
These individual formulation types are known in principle and are described, for example, in: Winnacker-Kiichler, "Chemische Technologie [Chemical Technology]", Volume 7, C. Hauser Verlag, Munich, 4th Ed., 1986; van Valkenburg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd., London.
The formulation auxiliaries required, such as inert materials, surfactants, solvents and other additives, are likewise known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldewell N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y. 1950; McCutcheon ' s , "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Sch6nfeldt, "Grenzflachenaktive Athylenoxidaddukte " [Surface-active Ethylene Oxide Adducts]", Wiss.
Verlagsgesellschaft , Stuttgart 1976; Winnacker-Kiichler, "Chemische Technologie [Chemical Technology]", Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986.
The invention therefore also relates to the agents which contain the compounds of the formula (I) according to the invention. These are mainly, on the one hand, plant-protecting agents which contain one or more compounds of the formula (I) and customary inert auxiliaries which are appropriate for the particular type of formulation, and, on the other hand, herbicidal agents which contain a combination of compounds of the formula (I) and one or more herbicides and customary auxiliaries which are appropriate for the particular type of formulation.
Combinations with other pesticidally active substances, fertilizers and/or growth regulators may also be prepared on the basis of these formulations, for example in the form of readymix or as a tank mix.
Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example polyoxethylated alkylphenols , polyoxethylated fatty alcohols and fatty amines, alkanesulfonates or alkylaryl-sulfonates, and dispersing agents, for example sodium ligninsulfonate, sodium 2 , 2 ' -dinaphthylmethane-6 , 6 '-disulfonate, sodium dibutylnaphthalenesulfonate, or alternatively sodium oleylmethyltaurinate , in addition to a diluent or inert substance.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene and also higher-boiling aromatic compounds or hydrocarbons, with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are: calcium salts of alkylarylsulfonic acids, such as Ca dodecylbenzene-sulfonate, or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products (for example block polymers), alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters .
Dusting agents can be obtained by grinding the active substance with finely divided solid substances, for example talc or natural clays, such as kaolin, bentonite, pyrophillite, or diatomaceous earth.
Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carriers, such as sand, kaolinites or of granulated inert material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or, alternatively, mineral oils. Suitable active substances can also be granulated in the manner which is conventional for the production of fertilizer granules, if desired in a mixture with fertilizers.
As a rule, the formulations according to the invention contain 0.1 to 99 % by weight, preferably 1 to 95 % by weight, in particular 2 to 90 % by weight, of active substance, i.e. active substance of the formula (I) or a combination of the active substance of the formula (I) with a herbicide.
The concentration of active substance in wettable powders is, for example, about 10 to 90 % by weight, the remainder to 100 % by weight is composed of conventional formulation components . In the case of emulsifiable concentrates, the concentration of active substance can be about 1 to 80 % by weight, preferably 5 to 80 % by weight. Formulations in the form of dusts mostly contain 1 to 30 % by weight, preferably 5 to 20 % by weight, of active substance, sprayable solutions about 0.2 to 25 % by weight, preferably 2 to 20 % by weight. In the case of granules, the active substance content depends partly on whether the active compound is liquid or solid and on which granulation auxiliaries, fillers etc. are used. In the case of water-dispersible granules, the active substance content is generally between 10 and 90 % by weight .
In addition, the active substance formulations mentioned contain, if appropriate, the adhesives, wetting agents, dispersing agents, emulsifiers, penetrants, solvents, fillers or carriers which are conventional in each case.
For use, the concentrates, present in commercially available form, are diluted, if appropriate, in a customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also in the case of microgranules . Preparations in the form of dusts or granulated preparations and also sprayable solutions are usually not further diluted with other inert substances before use.
The application rate required for the compounds of the formula (I) varies with the external conditions, such as, inter alia, temperature, humidity, and the nature of the herbicide used. It can vary within wide limits, for example between 0.005 and 10.0 kg/ha or more of active ingredient, preferably, however, it is between 0.01 and 5 kg/ha.
The examples which follow serve to illustrate the invention in greater detail: A. Formulation Examples a) A dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) or, if appropriate, a mixture of an active substance with a herbicide, and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill . b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I) or a mixture of (I) with a herbicide, 64 parts by weight of kaolin-containing quartz as the inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as the wetting and dispersing agent, and grinding the mixture in a pinned disk-mill. c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) or a mixture of (I) with a herbicide with 6 parts by weight of alkylphenol polyglycol ether (Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO = 8 ethylene oxide units) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277°C), and grinding the mixture in a ball mill to a fineness of below 5 microns.
An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) or a mixture of (I) and a herbicide, 75 parts by weight of cyclohexanone as the solvent and 10 parts by weight of oxethylated nonylphenol as the emulsifier .
A concentrate of a phenoxycarboxylic acid ester and an antidote (10:1) which is readily emulsifiable in water is obtained from 12.00 % by weight of ethyl 2-[4-(6-chlorobenzoxazol- 2-yloxy) phenoxy]propionate , 1.20 % by weight of compound of the formula (I), 69.00 % by weight of xylene, 7.80 % by weight of calcium dodecylbenzene- sulfonate, 6.00 % by weight of ethoxylated nonylphenol (10 EO) 4.00 % by weight of ethoxylated castor oil (40 EO) The preparation is carried out as indicated for Example a) .
A concentrate of a phenoxycarboxylic acid ester and an antidote (1:10) which is readily emulsifiable in water is obtained from 4.0 % by weight of ethyl 2-[4-(6-chlorobenzoxazol- 2-yloxy) phenoxy]propionate, 40.0 % by weight of compound of the formula (I) 30.0 % by weight of xylene, 20.0 % by weight of cyclohexanone, 4.0 % by weight of calcium dodecylbenzenesulfonate, 2.0 % by weight of ethoxylated castor oil (40 EO) .
B. Preparation Examples Example 1: Ethyl l-(2,4-dichlorophenyl)-5-isopropyl-5-methoxypyrazo-line-3-carboxylate 10 g of 2-methoxy-3-methylbut-l-ene and 10 g of triethyl-amine are heated at 80 °C. 15.5 g of the 2 , 4-dichloro-phenylhydrazone of ethyl 2-chloroglyoxalate (formula (II) with X1 = X2 = Y = CI, R1 = C2H5) (Ha) in 50 ml of toluene are added dropwise to this mixture within half an hour. Stirring is continued for 4 hours at 80 °C, the mixture is cooled, the precipitate is then filtered off with suction and the filtrate is concentrated in vacuo under mild conditions. After column chromatography (diluent petroleum ether/ethyl acetate 1:0 - - > 1:5) over silica gels 8.3 g of pyrazoline are obtained as an oil.
Example 2: Ethyl 1- ( 2 , 4-dichlorophenyl ) -5-ethoxy-5-isopropylpyrazo-line-3-carboxylate 6.2 g of 2-ethoxy-3-methylbut-l-ene and 6 g of triethyl-amine are initially introduced into 20 ml of cyclohexane at 70 °C; 15.0 g of compound (Ila) from Example 1 in 150 ml of cyclohexane are added dropwise over 1/2 hour. After 10 hours at this temperature, the precipitate is filtered off with suction and the filtrate is concentrated in vacuo. A precipitate of the product (9.2 g) of melting point 105 - 110°C is obtained as a solid from the mother liquor.
Example 3: Ethyl 1- ( 2 , 4-dichlorophenyl ) -5-methoxy-5-t-butylpyrazo-line-3-carboxylate 22.8 g of 3, 3-dimethyl-2-methoxybut-l-ene 15 g of potassium carbonate and 20 ml of dimethoxyethane are heated at 80 °C; 15 g of compound (Ila) from Example 1 in 100 ml of toluene are added dropwise at the same temperature over 1/2 hour. After stirring has been continued for 15 hours, the precipitate is filtered off with suction, the filtrate is concentrated in vacuo under mild conditions and the product is chromatographed as in Example 1. 10.7 g of product of melting point 130 - 133 °C are obtained.
The examples from Table I can be prepared analogously.
Table I: Alkoxypyrazolines of the formula Example 2,4-Cl2 n- C4Hg H oil CH3 CH3 i-C3H7 6 (CH2)2OCH3 CH3 1-C3H7 76- 78 7 C2H5 CH3 8 C2H5 CH3 C2H resin 4-C1-2-CF3 C2H5 CH3 i-C3H7 resin 0 2 -Br2 C2H5 CH3 i-C3H7- 1 , 547 1 2-CI-4-CF3 C2H5 CH3 1-C3H7 2 2 , 4-Cl2 C2H5 CH3 CH3 3 2,4-Cl2 n-C3H7 C2H5 H 4 n- C4H9 CH3 H 5 n-C5Hn CH3 CH3 6 i-C6H13 1-C3H7 H 7 cyclohexyl CH3 1-C3H7 8 cyciopentyi CH3 vinyl 9 CH3 n"c5Hll -C≡CH 0 CH3 i"C6Hi3 -C≡CH 1 (CH2)3OCH3 CH3 2 (CH2)2OC2H5 C2H5 C2H5 3 2,4- (CF3)2 CH3 CH3 CH3 4 C2H5 CH3 CH3 5 CH3 1-C3H7 6 2,4-F2 CH3 CH3 H 7 2-F-4-C1 CH3 CH3 H 8 2-F-4-CF3 C2H5 H 9 2,4-Br2 (CH2)2-OCH3 CH3 vinyl 0 4-Cl-2-CF3 CH3 H 1 2, -012 CH3 CH3 cyclohexyl 2 CH3 cyciopentyi 3 CH3 vinyl 4 " C2H3 2 -C1C2H4 H 5 C2H5 2 -CIC2H4 H 6 C2H5 3 -H-C3F6 H C. Examples of conversions into pyrazoles Example 1: Ethyl 1- ( 2 , 4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylate 10 g of pyrazoline from Example B.l are kept at 100°C for 2 hours and recrystallized from a little petroleum ether. 6.3 g of product having a melting point of 93 - 95°C are obtained as a solid (see note at the end of Example 2).
Example 2: 10 g of crude product from Example B.l (prior to column chromatography) are taken up in 150 ml of anhydrous toluene, and the mixture is refluxed with 0.5 g of p-toluenesulfonic acid for 4 hours. It is concentrated in vacuo and the product is recrystallized from a little petroleum ether. Yield 6.1 g, m.p. 93 - 95°C (note: the lower melting point of 70 - 77 °C which is indicated in P 3 808 896.7, Example 302, can be attributed to contamination with the isomeric pyrazole-3 ester.) D. Biological Examples Example 1 : In the greenhouse, wheat and barley were grown in plastic pots up to the 3- to 4-leaf stage and then treated post-emergence with the safener compounds and the tested herbicides. In these examples, the herbicides and the compounds of the formula (I) were applied in the form of aqueous suspensions or emulsions, and an amount of 800 1 of water/ha (converted) was used. 3 to 4 weeks after the treatment, the plants were scored visually for any type of damage by the herbicides applied, the extent of long-term growth inhibition being taken into account, in particular. The degree of damage or of safener action of compounds of the formula ( I ) , by themselves or in combination with herbicides, was determined in % damage.
The results show (cf. Table II) that the compounds according to the invention can effectively reduce exten-sive herbicide damage on crop plants.
Even in the case of massive overdoses of a herbicide such as fenoxaprop-ethyl , extensive damage of the crop plants is markedly reduced, and lesser damage is compensated completely. Mixtures of herbicides and compounds accord-ing to the invention are therefore suitable in an advantageous manner for selectively combating weeds in cereal crops .
Table II: Safener action Active Dose Herbicidal action ingredient/ [kg of a.i./ha] in % mixture of TRAE HOVU a . i .
H 2.0 75 — 0.2 - 80 H+Ex. 1 2.0 + 1.0 10 - 2.0 + 0.25 10 - 0.2 + 1.0 - 5 0.2 + 0.25 - 10 H+Ex. 10 0.2 + 1.25 - 17 Abbreviations : H = herbicide fenoxaprop-ethyl Ex. No. = see Example from Table I TRAE = Triticum aestivum (soft wheat) HOVU = Hordeum vulgare (barley)
Claims (12)
1. A compound of the formula (I) where X1 and X2 independently of one another are halogen or haloalkyl , R1 is hydrogen, alkyl, cycloalkyl or alkyloxyalkyl , R2 is alkyl, cycloaklyl or haloalkyl, and R3 is hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl, all geometric isomers and stereoisomers which are possible.
2. A compound of the formula (I) as claimed in claim 1, wherein X1 and X2 independently of one another are halogen or Ci-C-haloalkyl , R1 is Ci-C8-alkyl, C3-Ce-cycloalkyl or (Ci-Ce-alkyloxy) -Ci-Ce-alkyl, R2 is Ci-Cfj-alkyl, C3-Ce-cycloalkyl or Ci-Ce-haloalkyl and R3 is hydrogen, C^-Ce-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl or C2-C6-alkynyl .
3. A compound as claimed in claim 1 or 2, wherein X1 and X2 independently of one another are fluorine, chlorine, bromine or trifluoromethyl, R1 is Ci-C^-alkyl or (C1-C4-alkyloxy) which is unsubsti-tuted or monosubstituted or polysubstituted by halogen, and R3 is hydrogen, Cx-C^-alkyl, C2-C-alkenyl or C2-CA-alkynyl .
4. A process for the preparation of a compound of the formula (I) as claimed in clai 1, which comprises reacting a compound of the formula (II) - 20 - HOE 89/F 235 where Y is chlorine or bromine and X1, X2 and R1 are as defined above, with enol ethers of the formula (III) 0-R2 H2C= C ( I I I ) where R2 and R3 have the abovementioned meanings .
5. A plant-protecting agent which contains a compound of the formula (I), as claimed in one or more of claims 1 to 3, and inert carriers or other customary formulation auxiliaries .
6. A herbicidal agent which contains at least one compound of the formula (I), as claimed in one or more of claims 1 to 3, as safener, and a herbicide.
7. A herbicidal agent as claimed in claim 6, which contains, in addition, inert carriers or other customary formulation auxiliaries.
8. A herbicidal agent as claimed in claim 6 or 7, which contains a herbicide from the group of the carbamates, thiocarbamates , haloacetanilides , substituted phenoxy-, naphthoxy- and phenoxyphenoxycarboxylic acid derivatives, heteroaryloxyphenoxycarboxylic acid derivatives and dimedon-derived substances .
9. A method of protecting crop plants against phytotoxic secondary effects of herbicides, which comprises treating the plants, seeds of the plants or areas under cultivation with the compound of the formula (I) as claimed in - 21 - HOE 89/F 235 claim 1, 2 or 3, prior to, after, or simultaneously with, the plant protection agent.
10. The use of a compound as claimed in one or more of claims 1 to 3 as safener against phytotoxic secondary effects of plant protection agents.
11. The use of a compound of the formula (I) as claimed in one or more of claims 1 to 3 as an intermediate for the preparation of plant-protecting pyrazoles which have the corresponding structure.
12. A process for the preparation of plant-protecting pyrazoles of the formula where X1, X2, R1 and R3 are as defined in formula (I) as claimed in claim 1, which comprises treating the compounds of the formula (I) without or in the presence of an organic solvent, without or in the presence of an inorganic or organic acid, at temperatures between 0 and 200°C, during which process the compound of the formula HOR2, where R2 is as defined in formula (I), is eliminated. For Applicant -.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3923649A DE3923649A1 (en) | 1989-07-18 | 1989-07-18 | NEW PYRAZOLINE AND THEIR USE AS A SAFE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL95092A0 IL95092A0 (en) | 1991-06-10 |
| IL95092A true IL95092A (en) | 1994-06-24 |
Family
ID=6385232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL9509290A IL95092A (en) | 1989-07-18 | 1990-07-16 | 1-[(2,4- (Halo or haloalkyl substituted)-phenyl-5-cyclo-alkoxy]pyrazoline-3-carboxylates, their preparation and their use as safeners |
Country Status (19)
| Country | Link |
|---|---|
| US (2) | US5037468A (en) |
| EP (1) | EP0409118B1 (en) |
| JP (1) | JPH0352866A (en) |
| KR (1) | KR910002803A (en) |
| CN (1) | CN1048850A (en) |
| AU (1) | AU631227B2 (en) |
| BR (1) | BR9003443A (en) |
| CA (1) | CA2021343A1 (en) |
| DD (1) | DD296599A5 (en) |
| DE (2) | DE3923649A1 (en) |
| HU (1) | HUT55596A (en) |
| IE (1) | IE902606A1 (en) |
| IL (1) | IL95092A (en) |
| MA (1) | MA21905A1 (en) |
| NZ (1) | NZ234518A (en) |
| PL (1) | PL286094A1 (en) |
| PT (1) | PT94737A (en) |
| TN (1) | TNSN90102A1 (en) |
| ZA (1) | ZA905594B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3939503A1 (en) * | 1989-11-30 | 1991-06-06 | Hoechst Ag | NEW PYRAZOLINE FOR THE PROTECTION OF CULTURAL PLANTS AGAINST HERBICIDES |
| US5700758A (en) * | 1989-11-30 | 1997-12-23 | Hoechst Aktiengesellschaft | Pyrazolines for protecting crop plants against herbicides |
| DE4001600C1 (en) * | 1990-01-20 | 1991-03-07 | Hoechst Ag, 6230 Frankfurt, De | Pyrazole carboxylic acid derivs. prepn. - by reacting azo-carboxylic acid cpd. with an enol-ether and aromatising |
| JP3512196B2 (en) * | 1995-07-04 | 2004-03-29 | サントリー株式会社 | Food composition comprising a balance regulator for omega-6 and omega-3 unsaturated fatty acids |
| DE19739489A1 (en) * | 1997-09-09 | 1999-03-11 | Hoechst Schering Agrevo Gmbh | Process for the preparation of 1-phenylpyrazoline-3-carboxylic acid derivatives |
| JP4966454B2 (en) * | 2000-01-21 | 2012-07-04 | 石原産業株式会社 | Herbicidal microemulsion |
| KR100772226B1 (en) | 2004-12-07 | 2007-11-01 | 엘지전자 주식회사 | Prevent foreign material jams in the dishwasher |
| CN110922359A (en) * | 2019-11-28 | 2020-03-27 | 东北农业大学 | A kind of pyrazole derivative compound, preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1025430A (en) * | 1963-11-21 | 1966-04-06 | Ilford Ltd | Preparation of 3-pyrazolidinone derivatives |
| GB1500023A (en) * | 1975-01-31 | 1978-02-08 | Ici Ltd | Manufacture of 1-aryl-3-carboxy-pyrazolid-5-ones |
| IE59813B1 (en) * | 1986-05-09 | 1994-04-06 | Warner Lambert Co | Styryl pyrazoles, isoxazoles and analogs thereof having activity as 5-lipoxy-genase inhibitors and pharmaceutical compositions containing them |
| DE3808896A1 (en) * | 1988-03-17 | 1989-09-28 | Hoechst Ag | PLANT PROTECTION AGENTS BASED ON PYRAZOL CARBON SEA DERIVATIVES |
-
1989
- 1989-07-18 DE DE3923649A patent/DE3923649A1/en not_active Withdrawn
-
1990
- 1990-07-14 EP EP90113526A patent/EP0409118B1/en not_active Expired - Lifetime
- 1990-07-14 DE DE59007433T patent/DE59007433D1/en not_active Expired - Fee Related
- 1990-07-16 US US07/553,865 patent/US5037468A/en not_active Expired - Fee Related
- 1990-07-16 KR KR1019900010759A patent/KR910002803A/en not_active Withdrawn
- 1990-07-16 IL IL9509290A patent/IL95092A/en not_active IP Right Cessation
- 1990-07-16 MA MA22175A patent/MA21905A1/en unknown
- 1990-07-16 NZ NZ234518A patent/NZ234518A/en unknown
- 1990-07-17 AU AU59053/90A patent/AU631227B2/en not_active Ceased
- 1990-07-17 PL PL28609490A patent/PL286094A1/en unknown
- 1990-07-17 IE IE260690A patent/IE902606A1/en unknown
- 1990-07-17 BR BR909003443A patent/BR9003443A/en unknown
- 1990-07-17 ZA ZA905594A patent/ZA905594B/en unknown
- 1990-07-17 PT PT94737A patent/PT94737A/en not_active Application Discontinuation
- 1990-07-17 JP JP2187323A patent/JPH0352866A/en active Pending
- 1990-07-17 TN TNTNSN90102A patent/TNSN90102A1/en unknown
- 1990-07-17 CA CA002021343A patent/CA2021343A1/en not_active Abandoned
- 1990-07-18 CN CN90104762A patent/CN1048850A/en active Pending
- 1990-07-18 DD DD90342892A patent/DD296599A5/en not_active IP Right Cessation
- 1990-07-18 HU HU904534A patent/HUT55596A/en unknown
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1991
- 1991-06-27 US US07/722,534 patent/US5103017A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ZA905594B (en) | 1991-04-24 |
| NZ234518A (en) | 1993-04-28 |
| BR9003443A (en) | 1991-08-27 |
| PL286094A1 (en) | 1991-08-12 |
| JPH0352866A (en) | 1991-03-07 |
| CN1048850A (en) | 1991-01-30 |
| US5103017A (en) | 1992-04-07 |
| CA2021343A1 (en) | 1991-01-19 |
| EP0409118B1 (en) | 1994-10-12 |
| MA21905A1 (en) | 1991-04-01 |
| TNSN90102A1 (en) | 1991-03-05 |
| HUT55596A (en) | 1991-06-28 |
| DD296599A5 (en) | 1991-12-12 |
| IE902606A1 (en) | 1991-02-27 |
| DE59007433D1 (en) | 1994-11-17 |
| EP0409118A1 (en) | 1991-01-23 |
| US5037468A (en) | 1991-08-06 |
| AU631227B2 (en) | 1992-11-19 |
| HU904534D0 (en) | 1990-12-28 |
| KR910002803A (en) | 1991-02-26 |
| DE3923649A1 (en) | 1991-01-31 |
| PT94737A (en) | 1991-03-20 |
| AU5905390A (en) | 1991-01-24 |
| IL95092A0 (en) | 1991-06-10 |
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